High-quality Cu2ZnSnS4 (CZTS) thin films prepared by spray pyrolysis on a Mo-coated glass substrate were used for solar water splitting in this study. Modification of a CdS layer under CZTS improved the photocatalysis efficiency by forming a pn junction between CdS and CZTS, effectively separating the photoexcited carriers without recombination. However, the photocorrosive nature of CdS induces poor stability of the CdS/CZTS photocathode. Surface protection of a CdS-covered CZTS photocathode by a ZnS layer resulted in efficient photoelectrochemical water splitting with a maximum half-cell solar to hydrogen (HC-STH) efficiency of 2.1% and without showing appreciable degradation. The ZnS layer acts as a mediator for efficient electron transport to Pt deposits and as a protective layer, preventing contact between the CdS layer and the outer electrolyte solution. (C) 2018 Elsevier Inc. All rights reserved.